JPS5927935A - Bondable thermoplastic elastomer and its laminate - Google Patents

Abstract

PURPOSE:To provide the titled elastomer consisting of a blend of a oolyolefin resin, an ethylene/alpha-olefin compolymer rubber, etc. as well as a laminate useful for interior finish materials of automobile obtd. by laminating said elastomer layer onto a polyurethane foam layer. CONSTITUTION:25-200pts.wt. polyolefin resin is blended with 100pts.wt mixture consisting of a partially crosslinked ethylene/alpha-olefin copolymer rubber and an ethylene/alpha-olefin copolymer rubber having carboxyl groups or its anhydride groups in a weight ratio of 80/20-20/80 to obtain a bondable thermoplastic elastomer. The ethylene/alpha-olefin copolymer rubber having carboxyl groups or its anhydride groups can be obtd. by graft-copolymerizing an alpha, beta-unsaturated carboxylic acid or its anhydride. The bondable thermoplastic elastomer layer is laminated onto a polyurethane foam layer to obtain the titled laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to adhesive thermoplastic elastomers and laminates thereof. More specifically, we will focus on laminates effectively used as automobile interior materials and adhesive thermoplastic elastomers used in their construction.

For interior applications such as automobile floors, walls, and ceilings, the surface is embossed and embossed on the leather (consisting of a polyvinyl chloride layer with a texture, which is then covered with a foam layer and, if necessary, a resin layer). Laminates lined with sequential layers of aggregate have traditionally been used.

Such laminates are manufactured using the following techniques: (1) Calender molding of soft polyvinyl chloride to produce a sheet (2) Adding polyol and polyisocyanate to the surface of this sheet. The purpose of this matting treatment is to prevent the sheet surface from becoming glossy during thermoforming in step (7) described below (3). ) Embossing to form a grained leather pattern on the surface. (4) Flame-treating and melting the back side of the sheet with the embossed surface, and using a separately supplied polyurethane foam sheet and a four-wheel. (5) An adhesive layer is further provided on the polyurethane foam sheet side of the laminated sheet of the polyvinyl chloride sheet and the polyurethane foam sheet. (6) A thermoforming method such as vacuum forming or pressure forming is used to form a predetermined shape. Molding the resin aggregate (7) After preheating the polyvinyl chloride-polyurethane foam-adhesive laminated sheet, place it on the resin aggregate molded product. However, instead of such a polyvinyl chloride layer, polyolefin resins, ethylene and α-olefin, etc.
fi When using a single layer of thermoplastic elastomer made of a blend of a partially crosslinked synthetic rubber and an ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group, there are several problems in its production and properties. It was found that there was a significant deviation. That is, (a) such a laminate consists of a polyolefin resin, a partially cross-linked ethylene/α-olefin copolymer rubber, and a carboxyl group or its anhydride group-containing ethylene/α-
Olefin copolymer rubber blend about 150 to 250
The extruded thermoplastic elastomer in a molten state is passed between a pair of rolls while laminated with a polyurethane foam sheet, and the thermoplastic elastomer is extruded from an extruder at The rich elastomer sheet is made in contact with the embossing roll side at about 60-70°C, and the polyurethane foam sheet is brought into contact with the unheated normal roll side.

As a result, the steps corresponding to steps (1) to (4) described above when using soft polyvinyl chloride are performed in just one step, thereby providing a laminate with an embossed surface. That is, this laminate does not open during integral molding with an aggregate molded product by heating, which is performed later, so there is no particular need to provide a plowing step such as the step (2). In addition, in connection with this, in the case of polyvinyl chloride, in order to apply the matte treatment, it is necessary to form the polyvinyl chloride into a sheet shape in advance (as in the case of sanding), but the present invention If there is, tt[
It is possible to simultaneously (subsequently) fuse the polyurethane foam sheet with the polychloride resin for adhesion to the polyurethane foam sheet as seen in step (4) above. It also eliminates the need for processes such as flame treatment of vinyl sheets. Moreover, the embossing of the thermoplastic elastomer sheet can be carried out at the same time as the lamination with the polyurethane foam sheet, and the embossing process can be carried out at the same time as in step (3).
There is no need to provide a separate embossing process.

(b) Regarding the properties of the W1 layer, this laminate has excellent lightness, flexibility, and scratch resistance on the surface, and when soft polyvinyl chloride containing oJ plastic is used. There is no sticky feeling on the surface, and since thermoplastic elastomer and polyurethane foam both have excellent heat resistance, the laminate as a whole has excellent heat resistance.
Therefore, it can be effectively used as an interior material for automobiles, especially in the summer when the interior of the room becomes hot.

The present invention relates to an adhesive thermoplastic elastomer used to construct a laminate that is effectively used for such purposes,
This adhesive thermoplastic elastomer is composed of a blend of a polyolefin resin, a partially crosslinked ethylene/α-olefin copolymer rubber, and an ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group.

The present invention also provides a laminate comprising a thermoplastic elastomer layer made of such a blend and a polyurethane foam layer.

The adhesive thermoplastic elastomer according to the present invention is represented by the known thermoplastic elastomers listed below, namely (1) ethylene or propylene homopolymers or copolymers with small amounts of other polymerizable monomers. Various polyolefin resins and ethylene with 3 or more carbon atoms
A partially crosslinked blend of ethylene/α-olefin copolymer rubber, which is a binary copolymer rubber with 14 α-olefins or a ternary copolymer rubber obtained by further copolymerizing various polyene compounds with this rubber. (For example, see JP-B-53-21021 and JP-A-55-71738.) (6) A blend of a peroxide decomposable polyolefin resin and an ethylene/α-olefin copolymer comb. Thermoplastic elastomers obtained by dynamic heat treatment in the presence of organic peroxides (for example, Japanese Patent Publication No. 53-3421
Publication No. 0, Japanese Unexamined Patent Publication No. 149240, and Japanese Patent Application Laid-open No. 1983-149240.
3-149241) θj0 peroxide decomposition type poly]refin resin and ethylene α-]refin J
Cod' (combined Comte (7) blend was dynamically heat treated under organic peroxide (r: (E °C) and further blended with polyolefin 4I71I finger to give 71). For example, JP-A No. 53-145857'; J Publication and No. 54-
(Refer to Publication No. 16554)
Propylene is a peroxide crosslinked polyolefin resin represented by a co-in α form with a polymerizable monomer t form.

41-Cn single J of the pond,
Peroxide J1 represented by copolymer with VJ body, cross-linked polyolefin,
A blend of α-olefin copolymers is dynamically heat-treated (in the same way as a thermally treated plastic elastomer (see, for example, 1Q-111'l 55-71739)). J is made.

Specifically, polyolefin resin and ethylene α-4
It consists of a partially crosslinked product of fin copolymer rubber. ^CIj
pIJ echelastomer: I
0 Carboxyl group or its anhydride group. As the ethylene/α-olefin copolymer rubber containing , a copolymerization method known per se, a graft copolymerization method on ethylene/α-olefin copolymer rubber, etc.

α-olefins and shiteha copolymerized with ethylene etc.
Propylene, 1-butene, etc. are used, and monomer compounds containing a carboxyl group or its anhydride group include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, α,β-unsaturated carboxylic acids such as itaconic anhydride, unimic acid anhydride, and hymic anhydride, or their acid anhydrides are often used. Preferably, these (1,β-un#+i
741 carboxylic acid or its vinegar solution (It is an ethylene/α-]refin copolymer copolymer obtained by graft copolymerizing aqueous substances, and the obtained graft copolymer is slightly partially crosslinked,
'? There are also 1% and used in the same way. Other than this? Also used are lyolefins converted into C1 molecules and cal-4ζxylph^ introduced into the molecule.

ii. These copolymer rubbers may contain a polyene component, such as dicyclopentadiene, J, tylidene, l,4-hexadiene, etc. Generally, the copolymerization ratio is preferably 40 or less in terms of iodine value. In addition, ethylene and α-1-refin are about 50
The molar ratio of 150 to 9515 (-, commonly used,
#Sign.

These carboxyl group or anhydride group-containing ethylene/α-olefin copolymer copolymers generally have a Mooney viscosity pAL (at 100°C) of about 1 to 150, preferably about 1 to 100. River t/”E) tL
s Its carboxyl group (-〇〇〇〇),'+
It: The content of hydrate groups (calculated assuming that anhydride groups have two carboxyl groups) is generally about 0.
．． 02-10% by weight, preferably about 0.05-5% by weight
As mentioned above, these can be selected from a wide range within the range, and these may be partially crosslinked. The content of carboxyl groups in the blend is approximately 0.
．． 0.005 to 8% by weight, preferably about 0.1 to 4% by weight.
The ethylene/α-olefin copolymer rubber to be further further and partially cross-linked has a ratio of ethylene and α-olefin of about 50/150 to 90/10, preferably about 70/30 to 85/15, mainly for strength reasons. With a molar ratio of
It is desirable to use one having a knee viscosity M2+<(121°C) of about 20 or more, preferably about 40 to 80. In the case of this copolymer rubber, the same polyene component as described above may be copolymerized, and the amount thereof is preferably about 40 or less in terms of iodine value. Partial crosslinking of these ethylene/α-olefin copolymer rubbers is generally achieved by dynamic heat treatment using about 0.1 to 2 parts of organic peroxide per 100 ml of thermoplastic elastomer. will be carried out.

In the adhesive thermoplastic elastomer of the present invention, the partially crosslinked ethylene/α-olefin copolymer rubber and the ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group have a ratio of about 80/20 to 20/80. , preferably at a weight ratio of about 70/30 to 30/70, and about 25 parts of polyolefin resin per 10 parts by weight of the total amount of these.
It is used by blending it so that it occupies ~200 molding areas.

Adhesive thermoplastic elastomer)? - If necessary, peroxide non-crosslinked hydrocarbon-based rubbery substances such as polyisobutylene and butyl rubber and/or mineral oil-based softeners can be blended into the medium.

Polyurethane foam sheets laminated on one layer of adhesive thermoplastic elastomer made of such a blend include soft, semi-rigid, or hard foam sheets classified in terms of hardness;
Alternatively, any polynisder foam or polyether foam classified in terms of the polyol component can be used. In particular, when a soft foam having a nearly completely open cell structure is used, the laminate obtained therefrom is excellent in flexibility, heat resistance, sound absorption, etc. Further, the foaming ratio used is about 10 to 100 times.

The thus obtained laminate has excellent interlayer adhesion between the thermoplastic elastomer layer and the polyurethane foam layer, and it is possible to separate the two layers without breaking the polyurethane foam layer. Can not.

The laminate according to the present invention is generally laminated with a thermoplastic elastomer layer having a thickness of about 0.1 to 1 mm and a polyurethane foam layer having a thickness of about 0.5 to 20 mm. Compared to a laminate of vinyl and polyurethane foam, it is 17% lighter, has no problem of surface stickiness due to leaching of plasticizer, and has excellent heat resistance. It can be effectively used as a cover material for items such as furniture, building materials, first floors of houses, supplies), furniture, cabinets, sports equipment, office supplies, etc.

Next, the present invention will be explained with reference to two examples.

Example (component A) ethylene/propylene/5-ethylidene-2
-Norbornene ternary polymer; ethylene It position/propylene position (molar ratio)
: 78/22, iodine value 15, Mooney viscosity (ML
, +4.121°C) 61 (Component B) Isotactic polypropylene resin Melt index 1.3
97 iO min (230°C) (Component C) 1.3-Bis(tert-butylperoxyisopropyl)benzene 20 In Ml,%, Divinyl Penguin 30KnfR% and paraffinic mineral oil 50% by weight Bt% The above (component A) 70 if 11: Ffl<, (B
Combine 30 parts by mass of ingredients) and 11 parts by weight of (ingredients) in a Henschel-Michily/lIJ, then place the mixture in a closed Banbury mixer preheated to 12 () to 140°C. The mixture was then kneaded and crosslinked at 180 to 190°C for 10 minutes.

Thermoplastic elastomer 70f produced in this way
The T bottle part was made of maleic anhydride grafted ethylene/propylene copolymer rubber (ethylene/propylene molar ratio 80/20).
Toshiba y g
Using a Q mm diameter T-die extrusion molding machine, the screw was in full flight, L/D -22, extrusion temperature 220℃, T
- Extrude the adhesive thermoplastic elastomer in the form of a sheet using a two-toned die at a take-up speed of 25 m/min. 4 barrels)
The thermoplastic elastomer sheet is passed between a pair of rolls in a laminated state, with the thermoplastic elastomer sheet being brought into contact with the embossing roll side with a roll temperature fJF of 60°C, and the polyurethane foam sheet being brought into contact with the unheated normal roll side. Then, 1.4 pieces of pickles with a skin layer of Q and a thickness of 3 mm were prepared.

Example 2 Actual 11. I; In Example 1, instead of the maleic anhydride grafted ethylene/propylene copolymer rubber,
11℃ water maleic acid 7toethylene/1-butene copolymer comb (ethylene/1-butene mol Jt 90/10,
Mooney viscosity ML, +4 (12·1° C.) 4o, carboxylic acid content 0.5% by weight) was used.

Comparative Example 11 In Example 1, the produced plastic elastomer was extruded into a sheet without blending the maleic anhydride grafted polyethylene resin and laminated with a polyurethane foam sheet.

A test piece with a width of 25 mrn and a length of 100 m was cut from the laminated sheet obtained in each of the Examples and Comparison Examples described below, and was tested using an Instron tester to peel off T-beer.
Trial lv1! (Test HP speed 50 wz4), 1lill
A constant temperature of 25° C. was carried out. For each practical example, the adhesive strength was determined to be 2009/251r・ml or higher (polyurethane foam G!!I!ji), but the adhesive strength of the comparative example was 209/25. It was just the width.

agent Patent Attorney Yoshi 1) Toshio

Claims (1)

[Claims] 1. Adhesive thermoplastic comprising a blend of a polyolefin resin, a partially crosslinked ethylene/α-olefin copolymer rubber, and an ethylene/α-olefin copolymer rubber containing a carboxyl group or its anhydride group. Elastomer. 2. Ethylene/α-olefin copolymer rubber having carboxyl group or its anhydride group 75 (Ethylene/α-olefin copolymer rubber obtained by graft copolymerization of α, β-unsaturated carboxylic acid or its acid anhydride) Adhesive thermoplastic elastomer according to claim 1. 3. A thermoplastic elastomer made of a polyolefin resin, a thermoplastic-c elastomer made of a blend of ethylene/α-olefin copolymer rubber, and a polyurethane foam layer. Laminate. 4. α as an ethylene/α-olefin copolymer rubber having a carboxyl group or its anhydride group. Ethylene/α-olefin copolymerized by graft copolymerization of β-unsaturated carboxyl #/or its acid anhydride The laminate according to claim 8, wherein rubber is used.